The development of organic-inorganic photoactive materials has resulted in significant advancements in heterogeneous visible light photocatalysis. This paper reports the synthesis of visible light-active Ag/TiO2@Pani nanocomposite film via a simple biogenic-chemical route. Electrically conducting Ag/TiO2@Pani nanocomposites were prepared by incorporating Ag/TiO2 in N-methyl-2-pyrrolidone solution of polyaniline (Pani), followed by the preparation of Ag/TiO2@Pani nanocomposite film using solution casting technique. The synthesized Ag/TiO2@Pani nanocomposite was confirmed by UV-visible spectroscopy, photoluminescence spectroscopy, scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and thermogravimetric analysis. The Ag/TiO2@Pani nanocomposite film showed superior activity towards the photodegradation of methylene blue under visible light compared to Pani film, even after repeated use. Studies on the thermoelectrical behavior by DC electrical conductivity retention under cyclic aging techniques showed that the Ag/TiO2@Pani nanocomposite film possessed a high combination of electrical conductivity and thermal stability. Because of its better thermoelectric performance and photodegradation properties, such materials might be a suitable advancement in the field of smart materials in near future.